EP0625559B1 - Matériaux expansibles, leur préparation et utilisation - Google Patents

Matériaux expansibles, leur préparation et utilisation Download PDF

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Publication number
EP0625559B1
EP0625559B1 EP94301538A EP94301538A EP0625559B1 EP 0625559 B1 EP0625559 B1 EP 0625559B1 EP 94301538 A EP94301538 A EP 94301538A EP 94301538 A EP94301538 A EP 94301538A EP 0625559 B1 EP0625559 B1 EP 0625559B1
Authority
EP
European Patent Office
Prior art keywords
sealing material
blowing agent
material according
cavity
bubbled
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP94301538A
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German (de)
English (en)
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EP0625559A1 (fr
Inventor
Hajime Hasegawa
Kazuyoshi Usami
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Bridgestone Corp
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Bridgestone Corp
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Filing date
Publication date
Application filed by Bridgestone Corp filed Critical Bridgestone Corp
Publication of EP0625559A1 publication Critical patent/EP0625559A1/fr
Application granted granted Critical
Publication of EP0625559B1 publication Critical patent/EP0625559B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/30—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by mixing gases into liquid compositions or plastisols, e.g. frothing with air
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6204—Polymers of olefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/69—Polymers of conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K3/1006—Materials in mouldable or extrudable form for sealing or packing joints or covers characterised by the chemical nature of one of its constituents
    • C09K3/1021—Polyurethanes or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K2003/1034—Materials or components characterised by specific properties
    • C09K2003/1037—Intumescent materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K2200/02—Inorganic compounds
    • C09K2200/0239—Oxides, hydroxides, carbonates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
    • C09K2200/0645—Macromolecular organic compounds, e.g. prepolymers obtained otherwise than by reactions involving carbon-to-carbon unsaturated bonds
    • C09K2200/0652—Polyisocyanates
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S524/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S524/924—Treating or preparing a nonaqueous solution of a solid polymer or specified intermediate condensation product

Definitions

  • This specification relates to foamable and foam materials, e.g. such as are suitable to be put in a cavity of a pillar or another member in an automobile and heated for foaming into a polyurethane foam for sealing purposes. It also relates to the preparation and use of such materials.
  • Automobile center pillars and other frame members have a hollow cavity.
  • a foam for the purposes of preventing wind noise and absorbing vibration.
  • the cavity is filled with a foam by various methods. For example, foam previously shaped to the cavity shape is inserted into the cavity through an access opening.
  • a foamable material which is capable of foaming and expanding upon heating is placed in the cavity as a spot sealing material and later foamed to fill the cavity by heat encountered in a furnace for baking electrodeposited paint coating.
  • the former method of inserting a shaped foam body into a cavity has the problem that the cavity is filled to a varying extent partially because of insertion through an access opening. It is difficult to completely fill the cavity along its configuration from corner to corner.
  • the access opening which is often defined by punching out strip steel leaves a danger that the worker would have hands injured.
  • the general aim here is the provision of new foamable materials, new methods of preparing foamable materials, and new methods of filling or sealing using foamable materials.
  • Preferred aims are to achieve a high degree of expansion, and to achieve light weight (low density) of the material.
  • a particular aim is the application to fill a cavity in an automobile structural member, e.g. in a pillar.
  • a technique in which a liquid composition, containing polyurethane precursor compounds and a blowing agent, has bubbles of inert gas dispersed in it to give a bubbled composition.
  • a foam stabiliser may be needed to stabilise the dispersion of inert gas bubbles.
  • the resulting bubbled composition is then cured sufficiently to form a bubbled polyurethane material, but without or substantially without activating the blowing agent.
  • the blowing agent is adapted to be activated by heat, and the composition is cured by heat but at a temperature insufficient to activate the blowing agent.
  • the bubbled polyurethane is desirably a solid material which may be conveniently handleable. It may be tacky, which can be very useful in some applications. It may be provided with a release cover layer, for keeping until subsequent use.
  • the bubbled polyurethane material is treated - typically by heating to a sufficient temperature - to activate the blowing agent and make a foamed material e.g. for filling and/or sealing and/or insulation of sound or other vibration, or heat.
  • the expansion by the blowing agent is to at least twice and preferably at least five times the initial volume of the material.
  • the polyurethane-forming composition is selected so that the bubbled material will be capable of such expansion: this can be done without difficulty on the basis of the skilled person's knowledge of such compositions, and the disclosure herein.
  • the density of the bubbled polyurethane is preferably not more than 1g/cm 3 , that of the foamed material preferably not more than 0.2g/cm 3 .
  • Specific aspects herein include the above-described method as a whole, the method of making the bubbled polyurethane material, the bubbled polyurethane material itself, the method of making the foamed material from the bubbled polyurethane material e.g. in situ, and the foamed material itself.
  • Use of the material for sealing, filling or insulation is a further aspect, preferably with the foaming taking place in situ.
  • a material which is prepared by furnishing a liquid composition comprising a compound having at least two active hydrogen atoms, an organic polyisocyanate compound, a foam stabilizer and a blowing agent, dispersing inert gas in the liquid composition e.g. by mechanical agitation, to form a bubbled composition, shaping the bubbled composition into a predetermined shape, and curing the bubbled shape at a temperature below the decomposition temperature of the blowing agent.
  • the sealing material is disposed in a cavity of a pillar or another member in an automobile and heated for foaming to fill the cavity.
  • the material has a density of less than 1.0 g/cm 3 .
  • the compound having at least two active hydrogen atoms includes at least 50 parts by-weight of a polydiene polyol or polyolefin polyol terminated with a hydroxyl group per 100 parts by weight of the compound.
  • the liquid composition has an isocyanate index of 50 to 100.
  • a method for providing a seal or filling in a cavity includes the steps of disposing a material as defined above in the cavity, and heating the sealing material at a temperature equal to or above the decomposition temperature of the blowing agent for foaming and expansion, thereby filling the cavity with the foamed product.
  • the foamed product has a density not above 0.2 g/cm 3 .
  • the sealing material can be disposed in a cavity of a pillar or another member in an automobile and heated for foaming to fill the cavity. Since inert gas is previously dispersed through a liquid composition comprising a compound having at least two active hydrogen atoms, an organic polyisocyanate compound, a foam stabilizer, and a blowing agent by e.g. mechanical agitation, the resulting bubbled composition is lightweight and the bubbles therein are stable due to the presence of foam stabilizer.
  • the bubbled composition is shaped into a predetermined shape, for example, a sheet and thereafter, heat cured at a temperature below the decomposition temperature of the blowing agent into a foamable shape that is the sealing material.
  • this foamable shape or sealing material is heated at or above the decomposition temperature of the blowing agent, for example, during a paint coat baking or drying step, the blowing agent is decomposed to incur foaming.
  • This final foaming coupled with the previous uniform dispersion of inert gas bubbles, ensures a high blowing magnification. Therefore, the cavity in the automobile pillar or the like can be fully filled with a small amount of the sealing material.
  • the compound having at least two active hydrogen atoms includes at least 50% by weight, based on the weight of the compound, of a polydiene polyol or polyolefin polyol terminated with a hydroxyl group, the composition experiences greater volume expansion by decomposition gases of the blowing agent. Better blowing properties are obtained when the liquid composition has an isocyanate index of 50 to 100.
  • a sealing material proposed herein starts with a liquid composition comprising a compound having at least two active hydrogen atoms, an organic polyisocyanate compound, a foam stabilizer, and a blowing agent.
  • the compound having at least two active hydrogen atoms may be selected from liquid compounds usable, e.g. currently known for use, in the preparation of polyurethane, and reactive with organic polyisocyanate compounds.
  • liquid compounds usable e.g. currently known for use, in the preparation of polyurethane, and reactive with organic polyisocyanate compounds.
  • Preferred are polydienic polyols or polyolefinic polyols terminated with a hydroxyl group.
  • Preferred polydienic polyols terminated with a hydroxyl group are liquid ones having a number average molecular weight of 300 to 25,000, more preferably 500 to 10,000.
  • Exemplary are diene polymers having 4 to 12 carbon atoms, diene copolymers, and copolymers of such a diene monomer with an ⁇ -olefinic addition polymerizable monomer having 2 to 22 carbon atoms.
  • a useful polybutadiene type liquid rubber is commercially available under the trade name "Poly bd R-45HT" from Idemitsu Petro ⁇ Chemical Industry K.K.
  • Preferred polyolefinic polyols terminated with a hydroxyl group are as obtainable by polymerizing an aliphatic unsaturated hydrocarbon represented by the general formula C n H 2n having one carbon - to - carbon double bond in a molecule into an oligomer and introducing at least two hydroxyl groups per molecule in the oligomer by any desired method.
  • Preferred are polyols having a polyolefinic hydrocarbon skeleton such as polyethylene, polypropylene, polybutene, and polyisobutylene and having a molecular weight of 1,000 to 5,000. Most preferably, these polyols have a hydroxyl group introduced at either end.
  • the polydienic or polyolefinic polyol blended constitutes at least 50 parts by weight in 100 parts by weight of the compound having at least two active hydrogen atoms. This helps to assure adequate compression strength and appearance in the foamed product.
  • the organic polyisocyanate compound may be selected from compounds usable, e.g. currently known for use, in the preparation of polyurethane, for example, tolylene diisocyanate (TDI) and diphenylmethane - 4,4' - diisocyanate (MDI).
  • TDI tolylene diisocyanate
  • MDI diphenylmethane - 4,4' - diisocyanate
  • the liquid composition has an isocyanate index of 50 to 100, especially 70 to 90.
  • the bubbled composition may not be coagulative enough to shape.
  • the foam shape may be too coagulative to allow full expansion, and less tacky.
  • a foam stabilizer is usually desirable.
  • Suitable foam stabilizers are organic silicon surfactants. Suitable surfactants will be known to the skilled person. Useful organic silicon compounds are available under the trade names of L - 501, L - 520, L - 532, L - 540, L - 544, L - 3550, L - 5502, L - 5320, L - 5420, SZ - 1618, and Y - 6827 from Nippon Unicar K.K. and F - 114, F - 121, F - 305, and F - 317 from Shin-Etsu Silicone Co., Ltd.
  • a foam stabilizer is blended in amounts of 0.1 to 5 parts, especially 0.3 to 3 parts by weight per 100 parts by weight of the compound having at least two active hydrogen atoms.
  • the blowing agent is preferably selected from the substances which are decomposed by heating to generate carbon dioxide, nitrogen or other gas , preferably the substances which evenly generate gases at a temperature of about 130 to 210°C.
  • Suitable agents are known to the skilled person. Examples include azodicarbonamide, dinitrosopentamethylenetetramine, 4,4'-oxybis-benzenesulfonylhydrazide, azobisisobutyro - and para - toluenesulfonylhydrazide alone or a mixture thereof.
  • the blowing agent is preferably blended so as to provide a blowing magnification of at least 5, especially 6 to 30.
  • composition used as the raw material of the foamable shape of the present invention essentially contains the above - mentioned components while fillers, crosslinking agents, catalysts and other agents conventionally used in the preparation of polyurethane may be optionally blended.
  • the filler may be a conventional filler used in polyurethane, for example, calcium carbonate. It is preferred to blend less amounts of the filler in order to prevent the foamable shape from increasing its density. More particularly, the filler may be blended in amounts of 0 to 100 parts, especially 10 to 30 parts by weight per 100 parts by weight of the compound having at least two active hydrogen atoms.
  • Inert gas can be mechanically admixed into the liquid composition to provide a bubbled composition.
  • a bubbled composition is preparable by mechanically agitating an effectively inert gas (such as air, nitrogen or other gas without adverse reaction with the system) into the liquid by high shearing means such as Hobart mixer and Oakes mixer whereby the inert gas is uniformly dispersed as bubbles in the liquid phase comprising the active hydrogen-bearing compound, isocyanate and the like.
  • foam stabilizer helps to keep the bubbles stable.
  • the amount of inert gas introduced is not critical although the inert gas is preferably introduced such that the bubbled composition may have a density of less than 1.0 g/cm 3 , especially 0.3 to 0.95 g/cm 3 .
  • the bubbled composition may then be shaped into a predetermined shape to form a bubbled shape, and cured at a temperature below the decomposition temperature of the blowing agent.
  • the bubbled composition may be shaped to a configuration corresponding to the configuration of a cavity to be filled and the shaping method is not particularly limited. Often the composition is shaped into a sheet, for example, by passing the composition between spaced rollers along with release paper.
  • the bubbled shape should be cured at a temperature below the decomposition temperature of the blowing agent. Such curing is generally effected at about 40 to 90°C for about 5 to 20 minutes.
  • the bubbled shape after curing can constitute a sealing material.
  • the sealing material is disposed in a cavity to be filled and then heated at a temperature equal to or above the decomposition temperature of the blowing agent whereby the sealing material is foamed and expanded to fill the cavity therewith.
  • a predetermined amount of the sealing material is disposed in a cavity in an automobile pillar whereupon the material is foamed and expanded concurrently with the drying or baking step of electrodeposited paint coating.
  • the cavity is thus filled with the foamed product.
  • the foamed product has a density of up to 0.2 g/cm 3 .
  • the sealing material or cured bubbled shape may be attached to the inner wall of the cavity since it is preferably tacky. Since the sealing material is a bubbled shape having inert gas introduced therein, it is lightweight. Tackiness and light weight ensure that the sealing material, when attached to a vertical surface of the cavity inner wall, does not sag, slide down or fall down. Thus as long as the sealing material is disposed in place, the cavity can be fully filled with the foamed product.
  • Sealing material having such properties is advantageously used not only in filling cavities in automotive pillars and other members, but also for vibration damping in electric washing machines, refrigerators and air conditioners and for heat insulation and buffer in electric and other parts.
  • Such sealing material can be made with light weight and a high blowing magnification so that a large cavity can be filled with a relatively small amount (or lower weight) of the sealing material.
  • the foamed product resulting from this material is of quality. Sealing materials and methods disclosed herein may therefore be effective in reducing weight and cost and best suited for filling cavities in automotive pillars and other members.
  • Uniformly and finely bubbled compositions were prepared by blending a polyol, a polyisocyanate, a crosslinking agent, a catalyst, a silicone foam stabilizer, calcium carbonate, and a blowing agent as reported in Table 1 in an Oakes mixer and introducing air into the mixture while agitating.
  • Each bubbled composition was applied on release paper to a thickness of 2 mm by means of a roller and cured at 60°C for 15 minutes to produce a foamable sheet (sealing material) having uniformly distributed cells or bubbles. The density of the sheet was measured.
  • the foamable sheet was heated in a constant temperature over at 170°C for 15 minutes to produce a foamed product.
  • the foamed product was measured for blowing magnification, density and compression strength. The outer appearance was visually observed. The criteria for judging compression strength and appearance are shown below.
  • the Reference Example is a rubber-based foamed sealing material commercially available under the trade name of Therma-beta from Nitto Denko K.K.
  • the foamed products of 30 mm thick obtained in Examples 6 and 8 were measured for percent absorption of perpendicularly incident sound to find that they had better sound absorption over a wider frequency range than a conventional flexible polyurethane foam (specific gravity 0.02, 25% hardness 2 kgf).
  • the foamed product obtained in Example 8 was measured for transmission loss to find that it had an equivalent transmission loss over a wider frequency range as compared with a conventional asphalt ⁇ urethane integrally foamed product (density 0.1 g/cm 3 , 25% hardness 60 kgf).

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Sealing Material Composition (AREA)

Claims (11)

  1. Matériau d'étanchéité qui mousse lors du chauffage, pour l'utilisation dans le remplissage d'une cavité d'un montant ou d'une autre partie d'une automobile, ledit matériau d'étanchéité étant préparé par un procédé comprenant les étapes
    de fourniture d'une composition liquide comprenant un composé ayant au moins deux atomes d'hydrogène actifs, un composé organique de polyisocyanate, un stabilisant de mousse et un agent gonflant, et
    de dispersion uniforme d'un gaz inerte dans la composition liquide par agitation mécanique pour former une composition à bulles,
       caractérisé en ce que
       la composition à bulles est formée ou façonnée en un produit de forme prédéterminée et cuite par chauffage à une température inférieure à la température de décomposition dudit agent gonflant pour produire ledit matériau d'étanchéité expansible.
  2. Matériau d'étanchéité selon la revendication 1, dans lequel le produit de forme prédéterminée, cuit par chauffage, est collant.
  3. Matériau d'étanchéité selon la revendication 2, dans lequel ledit matériau d'étanchéité collant est muni d'une couche superficielle de séparation.
  4. Matériau d'étanchéité selon l'une quelconque des revendications précédentes, dans lequel ledit agent gonflant est adapté à générer du gaz à une température dans l'intervalle de 130 à 210°C.
  5. Matériau d'étanchéité selon l'une quelconque des revendications précédentes, dans lequel ledit composé ayant au moins deux atomes d'hydrogène actifs inclut au moins 50 parties en poids d'un polyol de polydiène ou d'un polyol de polyoléfine terminé avec un radical hydroxyle par 100 parties en poids dudit composé.
  6. Matériau d'étanchéité selon l'une quelconque des revendications précédentes, dans lequel ladite composition liquide a un indice d'isocyanate de 50 à 100.
  7. Matériau d'étanchéité selon l'une quelconque des revendications précédentes, qui a une densité inférieure 1,0 g/cm3.
  8. Matériau d'étanchéité selon l'une quelconque des revendications précédentes, dans lequel l'agent gonflant fournit une amplification par gonflement ou soufflage d'au moins 5.
  9. Matériau d'étanchéité selon l'une quelconque des revendications précédentes, dans lequel l'agent gonflant est l'azodicarbonamide, la dinitrosopentaméthylènetétramine, le 4,4'-oxybis-benzènesulfonylhydrazide, l'azobisisobutyronitrile, et le para-toluènesulfonylhydrazide, seuls ou en mélanges.
  10. Procédé pour fournir le remplissage de la cavité d'un montant ou d'une autre partie d'une automobile, comprenant les étapes de disposition d'un matériau d'étanchéité selon l'une quelconque des revendications 1 à 9 dans la cavité et le chauffage du matériau d'étanchéité à une température égale ou supérieure à la température de décomposition de l'agent gonflant pour mousser et expanser, remplissant ainsi la cavité avec le produit expansé.
  11. Procédé selon la revendication 10, dans lequel le chauffage dudit matériau d'étanchéité produit ledit produit expansé ayant une densité allant jusqu'à 0,2 g/cm3.
EP94301538A 1993-05-21 1994-03-03 Matériaux expansibles, leur préparation et utilisation Expired - Lifetime EP0625559B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP5142976A JPH06330021A (ja) 1993-05-21 1993-05-21 シール材及びシール方法
JP142976/93 1993-05-21

Publications (2)

Publication Number Publication Date
EP0625559A1 EP0625559A1 (fr) 1994-11-23
EP0625559B1 true EP0625559B1 (fr) 1998-06-03

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EP94301538A Expired - Lifetime EP0625559B1 (fr) 1993-05-21 1994-03-03 Matériaux expansibles, leur préparation et utilisation

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US (1) US5496868A (fr)
EP (1) EP0625559B1 (fr)
JP (1) JPH06330021A (fr)
DE (1) DE69410693T2 (fr)

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US10780672B2 (en) 2015-05-14 2020-09-22 Zephyros, Inc. Localized panel stiffener

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JP3409561B2 (ja) * 1996-02-19 2003-05-26 東海ゴム工業株式会社 車両用構造体の製造方法
FR2765227B1 (fr) * 1997-06-25 1999-08-20 Atochem Elf Sa Mousse flexible de polyurethane a base de polydiene hydroxyle
US6062624A (en) * 1998-04-21 2000-05-16 Lear Corporation Sealing acoustical baffle and method therefor
US6422575B1 (en) * 2000-03-14 2002-07-23 L&L Products, Inc. Expandable pre-formed plug
WO2003093064A1 (fr) 2002-05-02 2003-11-13 Dow Global Technologies, Inc. Comblement de cavites de carrosseries d'automobile
US9701093B2 (en) 2013-04-30 2017-07-11 Zephyros, Inc. Surface conforming activatable adhesive bodies and methods of making same
US10703036B2 (en) 2015-04-30 2020-07-07 Zephyros, Inc. Members for sealing, baffling, or reinforcing
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DE69410693T2 (de) 1999-01-07
JPH06330021A (ja) 1994-11-29
EP0625559A1 (fr) 1994-11-23
US5496868A (en) 1996-03-05

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